CN1300641A - Catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve - Google Patents
Catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve Download PDFInfo
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- CN1300641A CN1300641A CN 99122664 CN99122664A CN1300641A CN 1300641 A CN1300641 A CN 1300641A CN 99122664 CN99122664 CN 99122664 CN 99122664 A CN99122664 A CN 99122664A CN 1300641 A CN1300641 A CN 1300641A
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- catalyst
- acid
- molecular sieve
- alkoxylating
- cationic
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Abstract
A catalyst for alkoxylating solid acid with anion bonded chromatogrphy column molecular sieve is composed of active clay column supported L acid as active component and bonded anionic B acid. Said L acid is chosen from one or more kinds of Ti, Zr, Ce, Zn, Cu, Mg, Ag, Sn, Cu, Na, K and Mn. Said anionic B acid is chosen from one or more kinds of F, Cl, ClO4, SO42-, NO3-, PO43- and CF3COO-. Said active clay is chosen from one of montmorillonite and Ca-base bentonite. Its advantages are excellent reaction activity and selectivity, high effect on suppressing by-reaction, low cost and less environmental pollution.
Description
The present invention relates to alkoxylate L-B acid binding layered molecular sieve catalyst, a kind of C is provided especially
1～C
4Alcohol or mixed alcohol ethers and C
2～C
8The L-B acid binding layered molecular sieve catalyst that is better than general solid acid in the epoxide synthetic reaction.
At present, domestic and international C
1～C
4Alcohol or mixed alcohol ethers and reacting ethylene oxide all adopt NaOH, KOH or BF
3The etherate catalyst is made alkoxylating catalyst, although this reaction system has gratifying conversion ratio, also has many serious drawbacks:
(1) adopt alkali metal hydroxide to make catalyst, distribution of reaction products is wide, and the purpose selectivity of product is not high; Adopt alkaline earth metal hydroxide to make catalyst, though selectivity ratios alkali metal hydroxide catalyst selectivity height, Ba toxicity is big, Mg, and the Ca isoreactivity is not high, separates out easily, and reaction speed is too slow, and induction period is also longer.
(2) last handling process complexity, the three wastes of alkali metal hydroxide catalytic reaction products are more, and product loss is bigger.
(3) BF
3Et
2The O catalytic reaction, it is many to contain accessory substances such as diox and bis ether in the product, and equipment corrosion is serious, is difficult to obtain the product of 99% above purity.
The object of the present invention is to provide a kind of catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve, have good reactivity and selectivity, can effectively suppress to produce the side reaction in the alcohol ether process, reduce production costs, prevent equipment corrosion, reduce environmental pollution.
The invention provides a kind of catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve, it is characterized in that: this catalyst is by the pillared active constituent L of activated clay acid, and binding anion B acid constitutes; Active constituent L acid is selected from one or more of Ti, Zr, Ce, Zn, Cu, Mg, Ag, Sn, Cr, Na, K, Mn, accounts for catalyst gross mass 6-9%; Anion B acid is selected from F
-, Cl
-, ClO
4 -, SO
= 4, NO
- 3, PO
4 3-, CF
3COO
-One or more, account for catalyst gross mass 1-4%; Activated clay is selected from a kind of of imvite or calcium-base bentonite.
The imvite chemical composition is (m%) in the catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve of the present invention:
SiO
2???55～75％
FeSO
4??3～4％
Al
2O
3?7～13％
MgO?????2～3％
SnO?????0.2～0.3％
Main Ingredients and Appearance SiO wherein
2, Al
2O
3Deng, in course of reaction, can form stronger B acid site and L acid site, alkoxylation is had significantly be better than liquid acid BF
3Catalytic action, other component is a co-catalyst, plays synergy in course of reaction.
The preparation method of above-mentioned catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve is, with the calcium-base montmorillonite is raw material, make refining activated montmorillonite through wet concentration, pickling, washing, exchange with the L acid metal cation salt or the metal oxide aqueous solution then, make crosslinked layered molecular sieve, add B acid again and carry out binding, aging, filter, 110 ℃ of vacuum drying, 200～500 ℃ of roastings 1～6 hour, screening obtains catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve.
Among the preparation method of catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve provided by the present invention, slaine or metal oxide can be aluminum nitrate, ferric nitrate, cerous nitrate, lanthanum nitrate, copper nitrate, zirconium oxychloride, zirconyl nitrate, zinc nitrate, zinc oxide, zinc sulfate.
The present invention also provides catalyst at C
1～C
4Application in alcohol or mixed alcohol ethers and the oxirane synthetic reaction is characterized in that: reaction condition control is as follows:
A. material ratio: C
1～C
4The mol ratio of alcohol or mixed alcohol ethers and oxirane is 2～9, is preferably 3～8; Catalyst consumption is 3～10% of a material gross mass, is preferably 4～8%;
B. reaction process process: alkoxylation carries out on the device that the measurement volumes flow is arranged; The necessary anaerobic of reactor adds ormal weight C
1～C
4Alcohol or mixed alcohol ethers and catalyst purge reaction system in advance with nitrogen, start stirring; Add oxirane by charge pipe, finish reaction within a certain period of time, pressure is controlled at 0.2～0.3MPa, and temperature is as the criterion can absorb oxirane, is good with 30～200 ℃.
C. product analysis: the alkoxylated polymerization product of pure and mild oxirane HP-5890-II type chromatogram ration analysis, adopt 25mm * 0.32mm * 0.52 μ m * film thickness (Crosslinked Methyl Silicone Gum) chromatographic column, fid detector, nitrogen is carrier gas, 40～250 ℃ of column temperatures.
Use catalyst of the present invention to carry out alkoxylation and have following advantage:
(1) the reaction time weak point fed intake 30～40 minutes, and reaction can be finished, and the conversion ratio of oxirane is approaching
100％。
(2) catalyst activity height of the present invention, selectivity is good, and the monoalky lether yield reaches 88～95%.By-product in the reaction
The thing growing amount is less.
(3) catalyst of the present invention is easy to separate and reclaims, and can repeatedly recycle, and can add the alkali neutralization, directly
Go rectifying to separate.
(4) catalyst of the present invention does not corrode equipment, environmentally safe.
(5) imvite of catalyst use of the present invention, excellent performance, cheap.
When (6) the present invention carries out various reaction its technology simple, be easy to operate and control, intermittently or continous way give birth to
Produce all and be suitable for.
Catalyst provided by the invention particularly can be used for following reaction:
1. be raw material with methyl alcohol and oxirane (EO), the synthesizing glycol monomethyl ether.
2. be raw material with ethanol and EO, synthesizing glycol list ether.
3. be raw material with propyl alcohol and EO, synthesizing propanediol list propyl ether.
4. be raw material with butanols and EO, the synthesizing glycol monobutyl ether.
5. be raw material with glycol monoethyl ether and EO, synthetic diethylene glycol monomethyl ether.
6. be raw material with diethylene glycol monomethyl ether and EO, synthetic triethylene glycol monomethyl ether.
7. be raw material with ethylene glycol monoethyl ether and EO, synthetic diethylene glycol monoethyl ether.
8. be raw material with nROH/mROEOH and xEO, synthetic RO (EO)
2H, (R=Me, Et, n-Bu).[n/m=10～1，
Mol ratio, (n+m)/x=10～1]
9. with xROH/yROEOH/zRO (EO)
2H and nEO are raw material, synthetic RO (EO)
3H, (R=Me, Et, n-Bt).
[x/y/z=3-1/3-1/2-1, (x+y+z)/n=5～1, mol ratio]
Catalyst provided by the present invention is 88～95% to the selectivity of synthetic lower aliphatic alcohols series monoalkyl ethers (being target product), reaches and has surpassed the effect of boron trifluoride etherate as alkoxylating catalyst.The oxirane conversion ratio reaches 100%.
In order further to prove the fine quality of catalyst, adopt CH
3OH: the EO mol ratio is under the identical situation of 1: 1 and other condition, carries out the contrast test of ethoxylation with other type catalyst, and it the results are shown in Table 1.
Table 1 LB-1 type and other dissimilar catalyst alkoxylation situations
Reaction?conditions:?30～120℃,?CH
3OH/EO=1(molar?ratio),?0.1～0.4?MPa
| Catalyst type | Reaction temperature/℃ | Product quality mark/% selection/% | |||||||||
| Methyl alcohol | Glycol monoethyl ether | Diethylene glycol monomethyl ether | Triethylene glycol monomethyl ether | The TEG monomethyl ether | The five ethylene glycol monomethyl ether | Accessory substance | Glycol monoethyl ether | Diethylene glycol monomethyl ether | Triethylene glycol monomethyl ether | ||
| NaOH NaOCH 3BF 3·Et 2O PW 12LB-1 | 120 140 70 70 70 | 18.02 14.90 20.08 20.58 14.62 | 35.26 42.11 40.97 38.33 51.38 | 29.11 28.27 20.46 24.14 24.03 | 11.51 10.23 9.93 9.71 5.26 | 3.06 2.76 3.30 3.04 1.44 | 0.49 0.43 0.76 0.54 0.2 | 2.55 1.3 4.5 3.66 3.07 | 43.0 49.5 51.3 48.3 60.2 | 35.5 33.2 25.6 30.4 28.1 | 14.0 12.0 12.4 12.2 6.2 |
As shown in Table 1, with solid acid catalyst of the present invention (LB-1 type) preparation glycol monoethyl ether, main overall target is better than traditional NaOH, NaOCH significantly
3, BF
3Etherate and heteropoly acid (PW
12) catalyst.Prove also that simultaneously by the LB-1 type catalyst that contains microcellular structure of chemical modification preparation, in ethoxylation, its catalytic activity and selectivity can surpass homogeneous acid, base catalyst fully.
Embodiment 1:
Reaction mass is formed (mass ratio):
128 parts of methyl alcohol
22 parts in oxirane
4.5 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier with 4 parts of Ti (SO
4)
2Be dissolved in 50 parts of distilled water, add 20 parts of carrier activated montmorillonites under room temperature, stirred 1 hour, add H again
2SO
4Solution impregnation 72 hours adopts distilled water flushing, filters, puts into 300～400 ℃ of roastings of high temperature furnace 4 hours, and crushing screening to 200 order promptly forms LB-1 type catalyst.
Alkoxylation carries out on the device that the measurement volumes flow is arranged.Consider the security when using the oxirane operation, the necessary anaerobic of reactor, the methyl alcohol and the catalyst of adding ormal weight purge reaction system in advance with nitrogen, start stirring.Add oxirane by charge pipe, finish reaction within a certain period of time, pressure is controlled at 0.2～0.3MPa, and reaction temperature is 60～80 ℃.Glycol monoethyl ether selectivity 95% in the product that generates, diethylene glycol monomethyl ether is 4%, accessory substance bis ether etc. 0.3%.
Embodiment 2:
Reaction mass is formed (mass ratio):
184 parts of ethanol
22 parts in oxirane
6.8 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier with 4 parts of CuSO
4, be dissolved in 50 parts of distilled water, add 20 parts of carrier activated montmorillonites in stirring at room 1 hour, add H again
2SO
4Solution impregnation 72 hours adopts distilled water flushing, filtration, after 10 hours, adds 2 parts of BF 350 ℃ of roastings again
3/ absolute ethyl alcohol stirs 8h, filters, and 110 ℃ of dry 3h, crushing screening to 200 order promptly forms LB-1 type catalyst.
Alkoxylation carries out on the device that the measurement volumes flow is arranged.Safety when considering the operation of use oxirane is given birth to, the necessary anaerobic of reactor, and the ethanol and the catalyst of adding ormal weight purge reaction system in advance with nitrogen, start stirring.Add oxirane by charge pipe, finish reaction within a certain period of time, pressure is controlled at 0.2～0.3MPa, and reaction temperature is 65～85 ℃, ethylene glycol monoethyl ether selectivity 93% in the product of generation.Diethylene glycol monoethyl ether 4%, accessory substance bis ether etc. 0.4%.
Embodiment 3:
Reaction mass is formed (mass ratio):
296 parts in butanols
22 parts in oxirane
6 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier with 4 parts of ZnCl
2Be dissolved in the distilled water, add 20 parts of carrier activated montmorillonites, add H again in stirring at room 1 hour
2SO
4Solution impregnation 72 hours adopts distilled water flushing, filtration, after 48 hours, adds 2 parts of anhydrous AlCl 350～400 ℃ of roastings again
3/ n-butanol stirred 12 hours, and is aging, filter, and 110 ℃ of vacuum drying 8 hours, roasting 6 hours, crushing screening to 200 order promptly forms LB-1 type catalyst.
Alkoxylation carries out on the device that the measurement volumes flow is arranged.Consider the security when using the oxirane operation, the necessary anaerobic of reactor, the ethanol and the catalyst of adding ormal weight purge reaction system in advance with nitrogen, start stirring.Add oxirane by charge pipe, finish reaction within a certain period of time, pressure is controlled at 0.2～0.3MPa, and reaction temperature is 70～90 ℃, generates ethylene glycol monobutyl ether selectivity 91% in the product.Diethylene glycol monomethyl ether is 6%, accessory substance bis ether etc. 0.5%.
Embodiment 4:
Reaction mass is formed (mass ratio):
240 parts of n-propyl alcohol
22 parts in oxirane
5 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier with 4 parts of SnCl
4Add in 20 parts of carrier activated montmorillonites and the 100ml 2N hydrochloric acid,, add H again in stirring at room 1 hour
2SO
4Solution impregnation 72 hours adopts 200 milliliters distilled water flushing, filtration, after 48 hours, adds 2 parts of BF 350～400 ℃ of roastings again
3/ isopropyl alcohol stirred 12 hours, and is aging, filter, and 110 ℃ of vacuum drying 8h, roasting 6 hours, crushing screening to 200 order promptly forms LB-1 type catalyst.
Alkoxylation carries out on the device that the measurement volumes flow is arranged.Consider the security when using the oxirane operation, the necessary anaerobic of reactor, the n-propyl alcohol catalyst of adding ormal weight purges reaction system in advance with nitrogen, starts stirring.Add oxirane by charge pipe, finish reaction within a certain period of time, pressure is controlled at 0.2～0.3MPa, reaction temperature is 120～140 ℃, generate ethylene glycol ether selectivity 92.5% in the product, Diethylene glycol monopropyl ether is 6%, accessory substance bis ether etc. 0.7%.
Scale-up embodiment:
At 1m
3In the polymerization reaction kettle, add methyl alcohol 512kg, add the LB-1 type catalyst 10kg that embodiment 2 uses, under the mechanical agitation, use N
2Air is three times in the displacement still, is heated to 70 ℃, and beginning adds oxirane slowly, continuously.In this process, because of ethoxylation is heat release, the coiled pipe feeding cooling water frequently that is provided with in the still, control thermal balance, make to be reflected at 70-90 ℃ of interval and to carry out, add 88kg oxirane altogether, the reaction time is 2 hours, wore out 30 minutes at 80 ℃, stop to stir, discharging is filtered, catalyst is treated, and is reusable.The selectivity of glycol monoethyl ether is 94.5% in the product, and the selectivity of diethylene glycol monomethyl ether is 4.5%, accessory substances such as bis ether 0.3%.
Claims (5)
1 one kinds of catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve is characterized in that: this catalyst is by the pillared active constituent L of activated clay acid, and binding anion B acid constitutes; Active constituent L acid is selected from one or more of Ti, Zr, Ce, Zn, Cu, Mg, Ag, Sn, Cr, Na, K, Mn, accounts for catalyst gross mass 6-9%; Anion B acid is selected from F
-, Cl
-, ClO
4 -, SO
- 4, NO
- 3, PO
4 3-, CF
3COO
-One or more, account for catalyst gross mass 1-4%; Activated clay is selected from a kind of of imvite or calcium-base bentonite.
2. according to the described catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve of claim 1, it is characterized in that the imvite chemical composition is (m%):
SiO
2???55～75％
FeSO
4??3～4％
Al
2O
3?7～13％
MgO?????2～3％
SnO?????0.2～0.3％
3. the preparation method of the described catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve of claim 1, it is characterized in that: be raw material with the calcium-base montmorillonite, make refining activated montmorillonite through wet concentration, pickling, washing, exchange with the L acid metal cation salt or the metal oxide aqueous solution then, make crosslinked layered molecular sieve, add B acid again and carry out binding, aging, filter, 110 ℃ of vacuum drying, 200～500 ℃ of roastings 1～6 hour, screening obtains catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve.
4. according to the preparation method of the described catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve of claim 3, it is characterized in that: slaine or metal oxide are aluminum nitrate, ferric nitrate, cerous nitrate, lanthanum nitrate, copper nitrate, zirconium oxychloride, zirconyl nitrate, zinc nitrate, zinc oxide, zinc sulfate.
5. the described catalyst of claim 1 is at C
1～C
4Application in alcohol or the mixed alcohol ethers alkoxylation is characterized in that reaction condition control is as follows: (A) material ratio: C
1～C
4Alcohol or mixed alcohol ethers and C
2～C
8The mol ratio of epoxide is 2～9; Catalyst consumption is 1～5% of a material gross mass; (B) reaction process process: alkoxylation is to carry out on the device that the measurement volumes flow is arranged; Anaerobic in the reactor, the C of adding ormal weight
1～C
4Alcohol or mixed alcohol ethers and catalyst are used N
2Purge reaction system in advance, start stirring; Add epoxide by charge pipe; Reaction pressure is controlled at 0.2～0.3Mpa, and reaction temperature is 30～200 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99122664 CN1300641A (en) | 1999-12-22 | 1999-12-22 | Catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99122664 CN1300641A (en) | 1999-12-22 | 1999-12-22 | Catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve |
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|---|---|
| CN1300641A true CN1300641A (en) | 2001-06-27 |
Family
ID=5282648
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104138753A (en) * | 2014-07-29 | 2014-11-12 | 华南理工大学 | Tin-based montmorillonite catalyst, preparation method and application of tin-based montmorillonite catalyst for catalyzing xylose to prepare furfural |
| CN105457684A (en) * | 2015-12-15 | 2016-04-06 | 中山职业技术学院 | Hydrolyst, preparation method thereof and method for preparing butanedial |
| CN105498842A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst and application thereof |
| CN106914247A (en) * | 2017-03-16 | 2017-07-04 | 广西大学 | The preparation and application of a kind of nickel-base catalyst for carbon dioxide methanation |
-
1999
- 1999-12-22 CN CN 99122664 patent/CN1300641A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104138753A (en) * | 2014-07-29 | 2014-11-12 | 华南理工大学 | Tin-based montmorillonite catalyst, preparation method and application of tin-based montmorillonite catalyst for catalyzing xylose to prepare furfural |
| CN105498842A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst and application thereof |
| CN105498842B (en) * | 2014-09-25 | 2018-06-08 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst and its application |
| CN105457684A (en) * | 2015-12-15 | 2016-04-06 | 中山职业技术学院 | Hydrolyst, preparation method thereof and method for preparing butanedial |
| CN105457684B (en) * | 2015-12-15 | 2018-07-03 | 中山职业技术学院 | A kind of hydrolyst and preparation method thereof and the method for being used to prepare butanedial |
| CN106914247A (en) * | 2017-03-16 | 2017-07-04 | 广西大学 | The preparation and application of a kind of nickel-base catalyst for carbon dioxide methanation |
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